FeCl₃·6H₂O-Catalyzed Tandem Alkylation–Hydrolysis Reaction of Chain α-Oxo Ketene Dithioacetals with Alcohols: Efficient ­Synthesis of α-Alkylated β-Oxo Thioesters

Abstract

A novel FeCl₃·6H₂O-catalyzed tandem Friedel–Crafts alkylation–hydrolysis reaction between chain α-oxo ketene dithioacetals and alcohols to afford α-alkylated β-oxo thioesters has been successfully developed. The reaction is efficient in the presence of catalyst loading as low as 30 mol% in MeCN at room temperature, and a wide variety of α-alkylated β-oxo thioesters are efficiently synthesized in good yields.

Key words

tandem reaction - ferric chloride - thioester - ketene dithioacetal - Friedel–Crafts alkylation

• References and Notes

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• 17 Typical Procedure for the Preparation of α-Alkylated β-Oxo Thioester 3 The mixture of α-oxo ketene dithioacetals 1 (0.25 mmol), alcohols 2 (0.25 mmol), and FeCl₃·6H₂O (20 mg, 0.075 mmol) in MeCN (1 mL) was stirred for 10 h at r.t. Another 0.125 mmol of alcohols was then added, and the mixture was further stirred for 14 h at r.t. until 1 was completely consumed by TLC monitoring. The reaction mixture was then added to cold water (50 mL), and desired products 3 as a solid deposited from the reaction system. After filtered, the crude product 3 was purified by flash silica gel chromatography [PE (60–90 °C)–EtOAc, 15:1 v/v] to give pure 3 in good yield. Analytical Data of 3a Yield 87%; white crystalline solid; mp 150–151 °C. ¹H NMR (600 MHz, CDCl₃): δ = 7.97 (d, J = 7.7 Hz, 2 H), 7.55 (t, 1 H), 7.43 (t, 2 H), 7.36 (d, J = 7.7 Hz, 2 H), 7.28 (d, J = 7.5 Hz, 2 H), 7.21 (d, J = 7.4 Hz, 2 H), 7.18 (t, 1 H), 7.12 (t, 2 H), 7.04 (t, 1 H), 5.66 (d, J = 11.8 Hz, 1 H), 5.15 (d, J = 11.8 Hz, 1 H), 2.73–2.64 (m, 2 H), 0.97 (t, 3 H). ¹³C NMR (150 MHz, CDCl₃): δ = 193.0, 192.6, 141.5, 141.1, 136.8, 133.6, 128.8 (2 C), 128.7 (2 C), 128.6 (2 C), 128.5 (4 C), 127.8 (2 C), 126.8, 126.6, 67.1, 52.1, 23.9, 14.2. HRMS: m/z calcd for C₂₄H₂₂NaO₂S⁺ [M + Na]⁺: 397.1233; found: 397.1237.